Catalytic dehydration of organic compounds



cetes.

Fateuted dime $39, it 335 o rr ss ATENT QFFlC ALPEOHS (in JAEGEE, QB CEAFTQN, PENNSYLVANIA, ASSIGNOR- TO THE SELDEN COMPKAEPIY, @E IPI'ETSBUR-GH, PENNSYLVANIA, A CORPORATION 015 DELAWARE oerst'asro omrousrrou or ORGANIC consensus is Brewing. @riglual applicstics. filed April 3,

filed April 1, 1929.

This invention relates to catalytic dehydrations of organic compounds, such as, for example alcohols to unsaturated hydrocarbons.

According the present invention catalytic dehydrations of organic compounds are carried out particularly in the vapor phase by means of a new class of contact masses. The contact masses used in the present invention contain base exchange bodies or their derivatives. -"Under the term base exchange body are included all natural or artificial bodies which possess the properties of exchanging their bases for other bsses of salt solutions. lhe base exchanging products useo in making catalytic compositions ofthe present invention or as initial material for derivatives to be so used may possess high base exchanging power or in mes-y cases may possess lower base exchanging power, since the catalytic voice of the final compositions isriot primarily dependent on the of base exchanging power pres-e In general the exchange bodies may \3 divided into two categories z-t 'fl fi lllpfllltsllllarid molti-component zeo a, e., base exchange bodies containing'cr sally combined si con in their nucleus non-silicious base exchange bodies in vv :b all of the silicon is replaced by other suuoble acidic or amphoteric metal oxides. won 1 action products ponents, th:

using the broader ser in the dc a. type in silicate allot/e or multi-com products e cents, that least one in salt.

The base exchange bodies, both zeolites and non-silioious base exchange bodies, may be associated with .dilueuts preferebly in the form of s. physically homogeneous structure,

esvvill be described below. Either diluted lo sav, at Ha J. V 1 1-53mi, and e 1928, Serial No. 267,134. Divided and this application Serial No. 351,827.

or undiluated base exchange bodies may be present in the contact masses used in the pres ent invention, or their derivatives may be present, but it should be understood that whereier base exchange bodies are referred to both diluted and undiluted products are included.

'Base exchange bodies, both zeolites and non-silicious base exchange bodies, may also be transformed into derivatives which possess many of the chemical and most of the physical characteristics of the parentbase exchange bodies. Such derivatives may be salt-like bodies, that is to say, the reaction products of base exchange bodies with compounds containing anions capable of reacting with the base exchange bodies to form products which possess many of the properties of salts A further class of derivatives are the acid leached base exchange bodies. When a base exchange body is subjected to leaching by acids, particularly dilute mineral acids, the exchangeable bases are first gradually removed. The resulting products contain both the more basic and more acidic components of the non-exchangeable nucleus of the base er:- change body, with or Without a portion of the exchangeable bases. As the leaching; is carried on further, more and more of the relatively positive components of the nonexchangeable nucleus are removed, and it carried to completion the leached product contains only the relatively acid components of the non-exchangeable nucleus. lo the case of zeolites the final product :trom long continued leaching is a complex silicic acid which has many of the physical properties of the original base exchange body.

Catalytically active components may be associeted with diluted or undiluted permutd W use may be chemically combined with or in the permutogenetic products in non-exchangeable form, that is to say, they may form a part of the non-exchangeable nucleus of the base exchange body present in the final contact mass or which is transformed into the derivatives, or they may be chemically combined with the base exchange bodies in the form of catalytically active anions which form with the base exchange body salt-like bodies. (4) They may be chemically combined in exchangeable form either during the formation of the base exchange body or by base exchange after formation. Obviously of course the same or different catalytically active component may be' present in more than one of the above described forms, and it is an advantage of the present invention that catalytically active substances may be introduced in a Wide variety of forms which gives a large field of choice to the catalytic chemist.

While the difierent permutogenetic products may vary widely in their chemical characteristics, they all possess a similar physical structure which is characterized by more or less high porosity, frequently micro-porosity, and great resistance to high temperatures, and in the case of products which have not been acid leached to the point of removal of catalytically active components these components are distributed throughout the ramework of the products in atomic or molecular dispersion, as will be described in greater detail below, and this chemical homogeneity is one of the important advantages of some of the contact masses of the present invention.

While three of the methods of combination of the catalytically active substances may be efiected with undiluted as well as diluted permutogenetic products, it has been found that for most dehydration reactions homogeneously diluted permutogenetic contact masses are of advantage, particularly where the diluents are of a physical nature such as to exert a desired influence on a catalytic activity of the contact masses, as when, for example, diluents are rich in silica, which has been found to have an activating power, or where the diluents by reason of high porosity, capillarity, or surface energy may be considered as physical catalysts .or activators.

Base exchange bodies used in contact masses of the present invention behave as if they were products of extremely high molecular Weight for catalytically active components can be introduced either into the non exchangeable nucleus or in the form of exchangeable bases in practically any desirable proportions and the ordinary law of chemical combining proportions, which in compounds of low molecular weight restricts the proportions in which components can be incorporated chemically, appears to without-force, which makes it reasonable to assume that the molecular weight is so high as to completely mask the efi'ect of the law. It is of course possible that the base exchange bodies, or

some of them, may be solid solutions of a plu- V rality of related compounds of lower molecular weight. It has not been possible hitherto to definitely settle this question, as base exchange bodies are not readily capable of structural chemical analysis. The present invention is of course not limited to any theory, but irrespective of the underlying reasons the fact that catalytically active components may be chemically introduced in any desired proportions is of enormous importance to the catalytic chemist and gives him the power to produce an almost unlimited number of finely and gradually toned catalysts or contact masses for the dehydration of organic compounds and in all cases the contact masses produced are highly eliective by reason of the desirable physical structure of the permutogenetic products contained therein and the wide limits of homogeneous dilution of catalytically active molecules or atoms with resulting uniformity and smoothness of action, which is of great importance, particularly in the sensitive reactions for which contact masses used in the present invention are peculiarly adapted.

In addition to the important characteristics with which permutogenetic products endow the contact masses of the present invention, it has been found that for many of the reactions coming within the scope of the present invention it is desirableto stabilize the contact masses, and this may be effected by associating with the permutogenetic products or incor oratin or forming therein compounds 0 the a kali forming metals, that is to say, the alkali metals, the alkaline earth metals, and the strongly basic earth metals. These compounds appear to slow up or smooth out the catalytic reaction, and will be referred to throughout this specification as stabilizers. The stabilizers may be non-alkaline, weakly alkaline or strongly alkaline, depending on the reaction products and on the nature of the catalytically active components used. It is a great advantage of the present invention that in the normal formation of base exchange bodies alkali forming metal oxides are present as ex-v changeable bases, and whether used without acid treatment or treated with acid, they form stabilizers which are combined in or associated with the resulting permutogenetic Ill) products in an extremely fine state of division in which the stabilizers are peculiarly active. Thus, base exchange bodies containing alkali forming metal exchangeable bases may he considered as complex stabilizers.

In addition to the use of stabilizers, which are important in a large number of splitting reactions included in'the scope of the present invention, it has been found that the stabicific catalysts fox cice reaction is which they c invention be prepared by any of t are being used under the reaction cosditicns obtaining me be refereed. to thx'ougfsoue flee specification es ssebfiizer promoters es flsey appear to enhance the toning efieci; which can be ecllievecl To sisioflizersn The we cf this expression shclfld, @1Wiesel? in sense be taken to limit file expression is? theory oi sctioe cf these nen-spec e c212 eiysts anci in fact in some cases promoters may be presenewhei'eehere me me The tremendous megs cit chemicei groups which may he ccmbinefi with c1 imcorpcratedi in pemm neeic oroducts pecmias s wide chciee of seeciiizew romob es ysis, and permits theis the ccn tece messes e 31 homoge? indies or iheia as complex ceteaysis,

c 4. ebsse eziche ge isms-manila components or ini'siai me deriveeives conteci masses of ehe pres me well knewn methedls Thus, E01 ex 3' ewe-component zeolites be prepew L Wei", meihocls in which 'ehe neeefiefoe eempememes 01' metal seie components goes; cr 211 cf which may he ceteiycicafiy active, caused with soluble silicates fJc zeekiabes e? sis-mine silicate or sisminum doucie siiicsize eypes, or the cemeoeents may be i esefi pce'i-erebiy in flee picesence of fluxes, "lab shouifi be nnderst-ocd that unes she term meaallete is included 210 15 031337 the alkaline sohleions of amphotecic metal 031- ides or hydroxides but also alkali forming metei ecids, such as see 0137- scids eff mesels of the fifilh anti sixth groups, which in ea, least one stage of oxioehon are not strictbiy speaking amphoteric, but which proucis capable of reacting with silicates to form zeolites, or with other compenezcis form eon-silicious base exchange bodies, Threughoub the specificetien chis somewhsi; more general definition of messileises will be sfificfly adhered io. In the fee. me'iicn of ewe-composes; zeolites by Wet mezhos, resection produce must be alkaline licences, and for precincts of high base exchanging power it should! be neu'izrsl oz 21km e "(e phenciphfshalein. For the purpase preziucing base exchen e bociies the prepaza'bion 01 contact messes eesem invention is is sometimes en ecesssey "co pyevme high base #3; oman sew-e1 and for many purposes 289-.

e which is ecici phenoL cfjse 'ie li'emes are cf admin no, definiteiy known w? psoiucts ne'cdceed lander such circumstances enecus chests-cs3 cempounfis, s3-

easy ways they behave as o. reesce believe "31 as means see this -e pzefemecl apeosme piccons e ikeiimsy shoe w, I 02* many surgseses 1;; 3s

37 @1222. s oneecs zeoixes produced very c iepenieg en the preporizion components 'ihus,

e1 under conditions resulabing in see meiy com cs over the acidic thr and silicates predominate over the metallstes theproducts resemble the aluminum double silicate 1; pc of two-component zeolites; and, finally, i' the metallates and metal salts predominate over the silicates the resulting roduct resembles more or less non-silicious ase exchange bodies. lit will be clear that there is no sharp defining line between the three types or multi-cornponeni; zeolites, and

one shades to the other as the proportions of the i components vary. It IS an odvontog no multi-cornponent zeolites wocornponent zeolites that. the slyisicslly active components is cetclyticelly active elements il be incorporated in the ed others only in the "hemulti-coniponent yticqlly active group can ther 'nwhichitis best choice oi case exchange bodies are progcnerei methods described d of ringuig about resctions compos o or more oxynieizsl compounds to reset; in enersl,

least one metslla'ie and leest one s me'cl suit, or in some is o-ssible to bring choc. between allates i one -t is possible to pro- :s base exc bodies in h .413] of metal oxides is present. it is also to produce non-silicious base exciisnge bodies in which single motel is present. To. for example, some metals may be sufiici j l to form. both metell which are copsbie of reocting with co to reduce exchange bodies.

socciel rnebhod of producing non-silicious nose exchange bodies consists in the gradusl neutralization of trongly alkaline salts of the oxyccids of metal elements of the fifth and sixth groups stages of oxidation in which they are sufiiciently sniphoteric. The neutralization of other strongly slimline metallates also bring about forinstionof non-silicious base exchange bodies. The converse method, whereby non-alkaline salts of suitable metals are gradually crested with alkali until the reaction is sufficiently slimline to permit theformstirm of base exchange bodies, may also be used.

Many metals are capable of entering into the base exchange formation only in certain stages of oxidation, and ii; is sometimes necessary to introduce such metals in a stage of oxidation difierent from that desired in the final base exchange body, the change of stage of oxidation being preferably effected during the formation of the base exchange body. Certain otherelements may be incorporated in the form of complex compounds of the dues non 'cetelysts or activator most various types, such as; for example, ammonia, complexes and the hire.

In additionto the artificial base exchange,

' many dehydration reactions contain permutogenetic products in which preferably the diluents are homogeneously incorporated into the base exchange bodies before formation of the latter, or at leest before the base exchange body has set after formation. Many diluents, such as inert, stabilizing activating, cutslytically active, or having stabilizer promoter effects, can be used. A few of the diluents will be briefly enumerated kieselguhrs of all kinds, particularly natural or treated Celite esrth; si icious powders of various types; powdered permutogenetic products; nsturcl or artificial powders of rocks, stones, tulis, tress, love, and similarly volcanic products which are frequently highly porous; greensund; gleuconite or its acid leached derivative gluucosil; wool; ceine'ntsi sand; gel; pulverized earthenware; fullors esrth; talc; gloss powder; pumice meal; zisbc hos; graphite; activated carbon; quartz various pulverized minerals rich in quartz; motel powders and metal alloy powders; of oxynietnl acids such '33 tungststes, venadses, chroma'tes, ursnutes. mungenates, cerctes, molybdziies, etc, and particularly cooper solts of the above; silicates, such cs copper silicsfe, iron silicate, nickel siiic cobalt silicate, aluminum silicate, titsniuzc silicate; sls or ores, especially thos etc. inely divided diluen s advent-age, especially when the average particle size is less than microns, in which cos the diluents possess high. energy which increases the sdsorptive .und absorptive capacity of the contact mass, the diffusion speed and porosity. These finely divided diluents may be considered as physical Diluted permuto genetic bodies may also be finely divided used as part or all of the diluents of other base exchange bodies.

The following nine methods are the most effective for the introduction of diluents, but any other sui'toblemethods can be used.

l} The diluents may be mixed with one or more liquid components 01 the base exchange bodies to be formed when the letter are prepared by Wet methods.

(2) Components, either cstslyticelly active, stabilizer promoters, or others, may be precipitated or impregnated into diluent bodies which are then incorporated intothe base exchange bodies of any suitable methods of incorporation.

(3) Diluents may be mixed with base exchange bodies when the latter are still in noted with soiuti misc/2e the form of gels by @eading or stirring, in which case the base exchange gel behaves as an adhesive. The homogeneity and uniiormity oi the distribution of the diluents is of course not quite so great by this method. as toy Method (1), but for the dehydration of organic compounds extreme uniformity is not essential;

(d) Diluents may we formed during the formation of the loose exchange oodiesby mixing suitable compounds with the components oi the ense exchange bodies so tlnst the diluent particles are precipitated during formation. ii rctective colloids may be udded to prevent coagulation of the diiuent porticles before the tense exchange loodies have become suidciently (5} Gompounds. easy to added which reset with certain oi'tiie loose exchange bodies forming components to produce diinents, for

instance su ts oi the meta acids or the and sixth groups may ce mded suiiicient excess so that they react with components of the tease exchange body to form insoluiiie diluents, es, ior example, with oxides.

(tiiPreiormcd buss exciienge bodies, di- 1 d or undiluted, artificial. or can be impregnated with true or coiioidel sout-ions oi cetciyticciiy ettiecti e components end then dried.

1 c.) A preformed nose exchange too I,

l oi" undiinted, y be incuri iursiity of set s to precipitate o e {3} Solutoie diluent comgo l compounds, (ti) linturni nose iiciei base exchang pounds, which are then of reactive gases.

Tiie nucieus or non-enc osoi the moiecuies oi tl'ie ioese is ordineriiy considered to consi of two types o oxides, nsm y, reintiyeiy fsesic oxides, ususiiy emoiiot ric, iseistiveiy sci-die oxides, such as Si some photeiic metal oxides end some metni oxides wiiicii I have s distinctiy acid c'iisrocter, The nu= cleus believes es s single onion end cannot be split loy ordinary ciiemicoi means, nut is advantageous to considei" tire two 1 ortions oi the nucieus es the oesic-snd scidic "portions, bearing in mind of course that the nucieus e.- iinyes as e singie group, Tie metsi compounds which are capable of formingtheloosic portion of the nucieus ere tliose oi the foliowing meteis: copper, siivcr, goid, bismuth, 'foeryliium, zinc, cadmium, iooron, eluminum,

1 tiyeiy acid portion es the on genes s, iron, coiieit, ni indium, plstinum and cerium,

some rare earths, titanium, zirconium, tin, lead, thorium, niobium, antimony, tantalum, chromium, molybdenum, tungsten, uranium, vanadium, manganese, iron, nickel, cobalt, platinum, palsdium. Compounds of these elements may be introduced singly or in mix tures, in any desired proportions, and may he in the form of simple or complex ions. lit should be understood that some of the elements in certain stages of oxidation may be introduced either as metslletes or metal salts; others may be introduced in only one form; and still others may loe introduced in n stege of oxidation other than that desired in the finei hose exchange body, or in form of complex compounds. Among the compiex ionogens are ammonia, hydrocyenic acid, on alic acid, formic acid, tartaric acid, citric acid, glycerine, end the like.

Many of the metals are specific ceteiysts, others are stabilizers, and stiil others stabilizer promoters. Naturally the ststns of on element as catalyst or stabilizer moterwili vary with the particular reaction :too which the finsi contact moss is to ice used, end the choice of cetelystsoiid stabilizer pro motors, together with the proportions, Witt be determined by the particular organic dehydration reaction for which t to contoct moss is to be used.

"Examples of components iorrlno; to-

so nucieus are nikeii ineteisiiicetes y soluble in niiceii, and eliinii acids, such those of boron, p 3w nitrogen, tin, titanium, tun chromium, niobium, tent-elem, uranium, antimony, manganese.

The exciisngesbie osses of change Foodies may loe substi 1?" change, the elements no dnced singiy or in admixture loose on" change are the 'ioiio gold, ammonium, 'Eoery gonese, caesium, strontium, csdinuim, locriu scendiuin, titanium, zi co thorium, vanadium, ii liurn, bismuth, clirom Depending on the reactions in "-n contact is to to used, enciiengesbte i'Z-nses introduced mey "oe specific cntoiysts, they niey oe stcliilisers, or t ey' may so stoioiiizer promoters. Tiiey mo, intro duced as simple ions or its compi may enclience thecctniytic active finsi contact mess, improve its strength, or both.

As has ij-een described above, oose on change bodies can be caused to react with compounds containing acidic rediceis cope.- ole of forming therewith selt-iike Foodies. The rudicais may loe present in the form of simple acid radicals, polyacid radicals or complex acid radicals, and include radicals containing the following elements :chromium, vanadium, tungsten, uranium, molybdenum, manganese, tantalum, niobium, antimony, selenium, tellurium, phosphorus, bismuth, tin, chlorine, platinum, boron. Among the complex radicals are ferroand fen"- cyanogen. The amount of acid radicals caused to unite with the base exchange bodies to form salt-like bodies may be varied so that the resulting products may possess the charactor of acid, neutral or basic salts. Many of these acid radicals are stabilizers or stabilizer promoters for the dehydration of organic compounds.

The base exchange bodies, diluted or undiluted or some of their salt-like body dcrivatires, may be treated with acids, such as mineral acids, for example, 240% sulfuric, hydrochloric or nitric acids, to remove part or all of the eXchangeable buses, or also part or v all of the basic portion of the nucleus.

In the case of zeolites, the partial leaching with acids, which leaves part or all of the basic portion of the nucleus or even part of the exchangeable bases, does not atlect the function of the zeolites as catalysts when they contain catalytically active elements in the basic portion of the nucleus, or in some cases even exchangeable bases, and such partially leached catalysts are of great importance in many reactions. Where the leaching is carried out to completion the advantageous physical structure remains to a considerable extent the same but the remainder is of course a form of silica, or, in the case of zeolites in which part of the silica is replaced by other acidic compounds, a mixture of the two usually will not be specific catalyst for the reactions of the present invention. lit serves, however, as an advantageous physical carrier of specific catalysts, and in the case of partially substitutedzeolites may also contain stabilizer promoters.

Lcached non-silicious base exchange bodies, either partially or completely leached, may contain catalytically active components and behave as catalysts, stabilizer promoters, or both. and many important catalysts are thus obtained. This is particularly the case for reactions Wherea relatively alkali-free con:

tact mass is required for best results and Where the alkali content of a contact mass containing a base exchange body may be too great for optimum results.

Base exchange bodies or their derivatives, diluted or undiluted, may also be coated in the form of films on massive carrier granules or may be impregnatedtherein. The massive carriers may be inert, activating, or themselves catalysts. For example, certain catalytic metal alloys and minerals fall Within this class. Aluminum or copper alloy granules perform an additional advantageous function in that their relatively high heat conductivity tends to prevent local overheating in exothermic reactions, which is of considerable importance in obtaining good yields as many of the reactions, are equilibriumreactions, and at higher temperatures the equilibrium may be adversely afi'ected with resulting lowering of yields and contamination of the product.

Example The base exchange body produced by fus ing a mixture of 5 mols Na CO 1 mol .A .l303 3 mols 7H9 and 1 mol borax is care- ".1 ly leached with Warm water and then treated with a normal thorium nitrate solution in order to introduce a maximum of thorium oxide by base exchange. After drying me body is leached with dilute nitric acid in order to remove a maximum of the remaining alkali. This base exchange body may be used as is or may be powdered or coated onto carrier fragments by means of adhesives. Such fragments may be quartz filter stones, activated carbon, or fragments of oxide.

The contact mass can be readily used for the dehydration of alcohols to unsaturated. hydrocarbons. Thus, ethyl alcohol vapors "when passed over the contact mass at 34th- 380 are transformed into ethylene with good The dehydrations have been described as being carried out at ordinary pressure, which is the most economical in the majority or" cases. However, the reactions may be carried out elevated pressures or under a vacuum.

This application is a division of my prior application Serial l lo. 267,13, filed April 3, 1928..

l fhat is claimed as new is: Y 1. A method of dehydration, which corn-- prises subjecting an organic compound containing at least one hydroxyl group to the action or a contact mass containing a base exchange body.

2. A method of dehydration, which comprises vaporizing an organic compound containing at least one hydroxyl group and subjecting the vapors to the action of a contact mass containing a base exchange body.

3. method of dehydration, which comprises subjecting an organic compound containing at least one hydroxrl roup to the action of a contact mass containing a diluted base exchange body.

4.. A method of dehydration, which comprises vaporizing an organic compound containing at least one hydroxyl group and subjecting the vapors to the action of a contact m'ass containing a diluted base exchange body.

5. A method of dehydrating alcohols to unsaturated hydrocarbons, which comprises are vaporizingthe alcohol and subjecting the vapors to the action of a contact mass contammg a base exchange body.

6. A method of dehydrating alcohols to unsaturated hydrocarbons, whlch comprises vaporizing the alcohol and subjecting the vapors to the action'of a contact mass containing a diluted'base exchange body.

7. A method of dehydrating ethyl alcohol to ethylene which comprisesvaporizing the ethyl alcohol and subjecting the vapors /t0 the action of a contact mass containing a base exchange body.

8. A method of dehydrating ethyl alcohol to'ethylene, which comprises vaporizing the ethyl alcohol and subjecting the vapors to the action of a contact mass containing a diluted base exchange body.

9. A method according .to claim 1 in which at least one of the catalytically effective components is present in the ham exchange body in non-exchangeable form.

10. A method according to claim 2 in which at least one of the catalytically effective components is present in the base exchange body 111 non-exchangeable form.

11. A method according to claim 5 in which at least one of the catalytically efiective com ponents is resent in the base exchange body in non-exc angeable form. n

12. A method according to claim 7 in which at least one of the catalytically effective components is present in the base exchange body in non-exchangeable-form.

13. A method of dehydration which comprises subjecting an organic compound containing at least one hydroxyl groupto the action of a contact mass containing a compound included in the group consisting'of base exchange bodies, salt-like reaction products of base exchange bodies with metal acids, and acid-leached base exchange bodies.

' 14. A method of dehydrating alcohols to unsaturated hydrocarbons which comprises vaporizing the alcohol and subjecting the vapor to the action of a contact mass containing a compound included in the group consisting of base exchange bodies, salt-like reaction products of base exchange bodies with metal acids, and acid-leached base exchange bodies.

15. A method of dehydrating ethyl alcohol to ethylene which comprises vaporizing the ethyl alcohol and subjecting the vapors to the action of a contact mass containing a compound included in the group consisting of base exchange bodies, salt-like reaction products of base exchange bodies with metal acids, and acid-leached base exchange bodies.

Signed at Pittsburgh, Pennsylvania, this 28th day of March, 1929.

1 ALPHONS O. JAEGER. 

